CN102079938B

CN102079938B - High-temperature resistant non-sticking coating

Info

Publication number: CN102079938B
Application number: CN201010567017A
Authority: CN
Inventors: 刘海兵
Original assignee: HANGZHOU JIHUA POLYMER MATERIAL CO Ltd
Current assignee: HANGZHOU JIHUA POLYMER MATERIALS CO., LTD.
Priority date: 2010-11-29
Filing date: 2010-11-29
Publication date: 2012-10-17
Anticipated expiration: 2030-11-29
Also published as: CN102079938A

Abstract

The invention discloses a high-temperature resistant non-sticking coating, and belongs to the field of organic macromolecular compounds. The non-sticking coating contains 50 to 80 weight parts of organic silicon modified saturated polyester, 10 to 30 weight parts of high-temperature resistant pigment and filler and 5 to 10 weight parts of high-boiling solvent; the organic silicon modified saturated polyester is obtained by reaction of polyhydroxy branched saturated polyester and organic silicon resin intermediate in an amount which is 0.3 to 1.0 times weight of the polyester, wherein the hydroxyl value of the polyester is 120 to 200mgKOH/g, and the weight-average molecular weight is 2,000 to 6,000; and the weight-average molecular weight of the organic silicon resin intermediate is 800 to 2,000, the alkoxy content is 2.5 to 15 percent, and the hydroxyl content is 3 to 20 percent. The high-temperature resistant non-sticking coating has good heat resistance, non-sticking performance, good metal adhesion and low heavy metal content and harmful substance content, accords with restriction of hazardous substances (RoHS) instructions and standards, and is an environmentally-friendly product.

Description

A kind of high temperature resistant non-viscous paint

Technical field

The invention belongs to the organic high molecular compound field, relate to the macromolecular compound that only obtains, be specifically related to silicone resin with the silica reaction.

Background technology

Non-stick coating with a low surface energy and high heat resistance advantages, mainly coated cookware, appliances and other metal products surface, protect, loaded Chi, heat-resistant, non-stick, easy to clean and other functional effect.Non-viscous paint moment use temperature can reach 380 ℃, and the temperature of life-time service is between 180 ℃～250 ℃, thereby selected resin should have the characteristics of strong adhesion, Good Heat-resistance, hardness height, good mechanical property.Fire resistant resin mainly contains organic fluorine fire resistant resin and organosilicon fire-resistant resin.Organic fluorine has extremely good weather resisteant, pollution resistance, thermotolerance, chemical proofing, water-oil resistance etc., in fire resistant resin, occupies vital status.But organic fluorine costs an arm and a leg, and when having construction to processing requirements strictness, poor processability, the melt temperature height of ground be insoluble to shortcoming such as common solvent, thereby limited its application.Have in the silicone resin-the Si-O-Si-structure, demonstrate performances such as good weathering resistance, thermotolerance, anti-stain characteristic and chemically stable.But pure silicone resin needs hot setting, and long construction inconvenience set time, and with the poor adhesive force of metallic substance, poor solvent resistance, physical strength are not high, so its use receives restriction to a certain degree simultaneously.With other resins such as vinyl resin and epoxy resin silicone resin is carried out chemical modification, can improve the performance of silicone resin.But the metal poor adhesive force of acryl-modified silicone resin resin can not satisfy the requirement of non-viscous paint; The shock resistance and the hardness of epoxy resin modified organosilicon resin are low, all can not satisfy the requirement of non-viscous paint.

Pigment and filler are the important component parts of non-viscous paint, influence resistance toheat, mechanical property and the solvent resistance of non-viscous paint, and simultaneously pigment and filler are the main sources of heavy metal and objectionable impurities in the non-viscous paint.Mostly the heat resistant pigment that traditional coating uses is bright-coloured MOX and salt such as red, yellow, blue, green, has low price, and color is various in style, the advantage that resistance toheat is good; But there are dispersing property difference and the low shortcoming of resin affinity.And traditional heat-resisting mineral dye contains heavy metals such as lead, cadmium, chromium, influences its application on non-viscous paint.

Summary of the invention

The technical problem that the present invention will solve provides a kind of non-viscous paint, and this non-viscous paint has resistance to elevated temperatures, and its objectionable impurities and heavy metal content are low, meets RoHS instruction and standard.

For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:

A kind of high temperature resistant non-viscous paint, this coating contain the organic-silicon-modified saturated polyester of 50～80 weight parts, 10～30 weight part high-temperature resisting pigment fillers and 5～10 weight part high boiling solvents; Wherein,

Described organic-silicon-modified saturated polyester is to be obtained by poly-hydroxy branching saturated polyester and poly-hydroxy branching saturated polyester weight 0.3～1.0 times silicone resin midbody reaction; Wherein,

Described poly-hydroxy branching saturated polyester is to be reacted by 0.8～0.9 times polyvalent alcohol esterification of a benzene diformazan and m-phthalic acid amount of substance to obtain, and its hydroxyl value is 120～200mgKOH/g, and weight-average molecular weight is 2000～6000; Wherein, described polyvalent alcohol is by the NSC 6366 of 60～80 moles of %, the 2-methyl isophthalic acid of 15～35 moles of %, and the TriMethylolPropane(TMP) of 3 Ucar 35 and 1～10 mole of % is formed;

The weight-average molecular weight of described silicone resin midbody is 800～2000, and contains 2.5～15% methoxy or ethoxy and 3～20% hydroxyl.

Silicone resin midbody of the present invention can be by the monomethyl triethoxyl silane; Dimethyldiethoxysilane; The condensation reaction that is hydrolyzed of siloxanes such as one phenyl triethoxy obtains; Also can be by the monomethyl Trimethoxy silane, dimethyldimethoxysil,ne, the condensation reaction that is hydrolyzed of siloxanes such as a phenyl trimethoxy obtains.

The siloxanes of the present invention condensation reaction that is hydrolyzed is the condensation reaction that is hydrolyzed of this area siloxanes commonly used, and its technology and reaction conditions are the routine techniquess that those skilled in the art should grasp.

The KR9218 of the IC836 of Wa Ke company of the KR214 of the KR211 that silicone resin midbody of the present invention can also be a company of SHIN-ETSU HANTOTAI, the KR212 of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI, the KR216 of company of SHIN-ETSU HANTOTAI, Wa Ke company, the KR213 of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI, the KR217 of company of SHIN-ETSU HANTOTAI, Dow Corning Corporation 233, Dow Corning Corporation 249,3074 and Dow Corning Corporation of the Z-6108 of Dow Corning Corporation, Dow Corning Corporation 3037 in a kind of or two or more.

High boiling solvent of the present invention is a kind of or two or more in divalent ester mixture (DBE), ethylene glycol ether acetate (CAC), Diethylene Glycol monobutyl ether acetate (DBA), isobutyl isobutyrate, propionic acid-3-ether ethyl ester (EEP) and the methyl isoamyl ketone (MIAK).

Pigment of the present invention is a kind of or two or more in pigment yellow 13 9 (CAS36888-99-0), Pigment Yellow 73 180 (CAS77804-81-0), Pigment red 254 (CAS84632-65-5), phthalocyanine blue (CAS147-14-8), phthalocyanine green 7 (CAS1328-53-6) and the pigment red 122 (CAS No:16043-40-6).

Filler of the present invention be titanium oxide or and silicon-dioxide.

The preparation method of organic-silicon-modified saturated polyester resin of the present invention is this area preparation method commonly used, is about to silicone resin midbody and poly-hydroxy branching saturated polyester and under the katalysis of isocaprylic acid zinc, dewaters, takes off ethanol or methyl alcohol obtains.

Organic-silicon-modified saturated polyester resin of the present invention also can be prepared by following method:

At first polyvalent alcohol is added and be equipped with in the reactor drum of heating, condensation and nitrogen protection, under nitrogen protection, be warmed up to 160 ℃, polyvalent alcohol is melted; Add polyprotonic acid and tetrabutyl titanate then, heating also in temperature does successively, 180～220 ℃ of down insulations 4 hours, 220～240 ℃ of insulations 2 hours down, 240～260 ℃ of insulations 2 hours down; Be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 50～80w%, cool to room temperature;

With in the poly-hydroxy branching saturated polyester, silicone resin midbody and isocaprylic acid zinc mixes; Under nitrogen protection, be warmed up to 120 ℃ of insulations 2 hours; Be warmed up to 160 ℃ of insulations 2 hours, last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60w%.

High temperature resistant non-viscous paint of the present invention can also contain auxiliary agents such as skimmer, viscosity modifier, dispersion agent.

The preparation method of high temperature resistant non-viscous paint of the present invention is this area preparation method commonly used, that is, described organic-silicon-modified saturated polyester, paint filler and high boiling solvent mixed get final product.

High temperature resistant non-viscous paint of the present invention has good heat-resistant, is not stained with performance and good metal sticking power; And heavy metal content and harmful substance contents are low; Meet RoHS instruction and standard, can be widely used on the hardware products such as sandwich baking tray, waffle baking tray, coffee pot, stove and accessory surface, cake mould, barbecue grill, electriciron, cooker inside and outside wall, electric cooker, bread producing machine.

High temperature resistant non-viscous paint of the present invention with organic-silicon-modified saturated polyester as base resin; With tetrazo class, the different diindyl quinoline ketone, 2 that draws; Pigment dyestuffs such as 9-dimethylquinacridone, pyrrolopyrrole diketone are as pigment; With titanium oxide and silicon-dioxide as filler; Organic-silicon-modified saturated polyester is combined the advantage of vibrin and the advantage of silicone resin, and resulting coating has the high advantage of good weathering resistance, thermotolerance, anti-stain characteristic, chemicalstability, solvent resistance and physical strength.

Pigment and filler are the chief components of non-viscous paint, its effect be not limited only to painted with reduce cost, also have strengthening action, improve the sticking power film, hardness, performance such as shock-resistant.Request for utilization according to non-viscous paint; Pigment and filler should possess following four conditions: (1) good heat resistance; Stable performance at high temperature can reach 380 ℃ because be coated in interior temperature of the paint filler short period of time of product surface, and the temperature of life-time service is about 180 ℃～250 ℃; (2) good with the consistency of polyester modification silicone resin, and be prone to and the filming of polyester modification silicone resin formation form compact and stable, the resistance toheat and the mechanical property of filming can be improved; (3) heavy metal content and harmful substance contents are low, meet RoHS instruction and standard.The present invention selects tetrazo class, the different diindyl quinoline ketone, 2 that draws, and pigment dyestuffs such as 9-dimethylquinacridone and pyrrolopyrrole diketone are as pigment, and titanium oxide and silicon-dioxide can satisfy above-mentioned four conditions as filler.

High temperature resistant non-viscous paint of the present invention compared with prior art has the following advantages:

(1) adopt organic-silicon-modified saturated polyester as base resin; Tetrazo class, the different diindyl quinoline ketone, 2 that draws; Pigment dyestuffs such as 9-dimethylquinacridone, pyrrolopyrrole diketone are as pigment; Titanium oxide and silicon-dioxide is as filler, films to have good heat-resistant, be not stained with performance, hardness and sticking power.

(2) heat-proof non-stick coating of the present invention is nontoxic, does not contain the compound of halohydrocarbon, benzene,toluene,xylene, formaldehyde and heavy metal lead thereof, cadmium, chromium, mercury, and its heavy metal and harmful substance contents meet ROHS instruction and standard, belong to Green Product.

Embodiment

Below be specific embodiment of the present invention, but be not limited to said embodiment.

Embodiment 1

1) poly-hydroxy branching saturated polyester is synthetic

A) raw material:

NSC 6366 62.4g (0.6mol);

The 2-methyl isophthalic acid, 3 Ucar 35 27g (0.3mol);

TriMethylolPropane(TMP) 13.4g (0.1mol);

M-phthalic acid 132.8g (0.8mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.4g tetrabutyl titanate then, heating also in temperature does successively, 180 ℃ of down insulations 4 hours, 220 ℃ of insulations 2 hours down, 240 ℃ of insulations 2 hours down; Be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 349g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 140mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 3442.

2) the silicone resin midbody is synthetic

A) raw material

Monomethyl triethoxyl silane: 67.64g (0.38mol)

Dimethyldiethoxysilane: 29.6g (0.2mol)

One phenyl triethoxy: 172.8g (0.72mol),

B) preparation technology

After in the reactor drum that prolong, TM, tap funnel and whisking appliance are housed, adding siloxanes and 7.8mmol hydrochloric acid successively, begin to stir and heat up, keep homo(io)thermism after being warmed up to 65 ℃ by proportioning; Under agitation drip 39.9g zero(ppm) water, after dropwising, again behind the isothermal reaction 3h; The beginning underpressure distillation, pressure-controlling boils off the small molecules that produces in the reaction process at 0.06MPa; Cool to room temperature, the adjustment solid content is 60%, obtains silicone resin midbody 361g.

C) performance:

R/Si＝1.15；ph/Me＝0.93；

The weight-average molecular weight of silicone resin midbody adopts gel permeation chromatography, and the result is 1854; The hydroxy radical content of silicone resin midbody adopts the diacetyl oxide method to measure, and the result is 18%; The oxyethyl group content of silicone resin midbody adopts perchloric acid acetyl method to measure, and the result is 8.4%;

3) preparation of organic-silicon-modified saturated polyester

A) raw material:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 150g;

The silicone resin midbody of 60% solid content of above-mentioned steps 2 preparations: 150g;

B) preparation technology:

The poly-hydroxy branching saturated polyester of above-mentioned steps 1 preparation and the silicone resin midbody adding of above-mentioned steps 2 preparations are equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 4g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 316g.

4) high temperature resistant non-viscous paint

A) raw material

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 3 preparations: 100g;

Pigment yellow 13 9:12g;

Titanium oxide: 5g;

Divalent ester mixture (DBE): 10g.

B) preparation of non-viscous paint

Paint filler, organic-silicon-modified saturated polyester and high boiling solvent are mixed, add grinding machine for grinding, obtain non-viscous paint to required particle diameter.

C) performance of non-viscous paint

The paint film preparation is undertaken by the regulation of GB/T 1727-1992.During the sample making of test, condition of cure is 380～400 ℃ and solidified 10 minutes that its performance is as follows:

The over-all properties of table 1 non-viscous paint

Resistance toheat: test piece behind 180 ℃ of baking 2h, is put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min elevated temperature; Pick up counting to the requirement of experiment temperature with furnace temperature, sample takes out through behind the continuous high temperature; Be chilled to room temperature (25 ℃); Observe the coatingsurface situation with reading lens,, explain that promptly coating heat resistance can be good as not having be full of cracks, obscission; Anti-yellowing property: test piece behind 180 ℃ of baking 2h, is put into 400 ℃ of baking ovens, take out after 5 minutes, be chilled to room temperature, observe color and whether change, jaundice.

Embodiment 2

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 83.2g (0.8mol);

The 2-methyl isophthalic acid, 3 Ucar 35 13.5g (0.15mol);

TriMethylolPropane(TMP) 6.7g (0.05mol);

M-phthalic acid 149.4g (0.9mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.4g tetrabutyl titanate then; Heating also in temperature does successively, and 190 ℃ of down insulations 4 hours are heated to 230 ℃ of insulations 2.5 hours down then, 260 ℃ of heating 2 hours down; Reach 91% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 347g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 120mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 5230.

2) the silicone resin midbody is synthetic

A) form

Monomethyl triethoxyl silane: 44.5g (0.25mol)

Dimethyldiethoxysilane: 50.3g (0.34mol)

One phenyl triethoxysilane: 98.4g (0.41mol),

B) preparation technology

After in the reactor drum that prolong, TM, tap funnel and whisking appliance are housed, adding siloxanes and 7.0mmol hydrochloric acid successively, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃ by proportioning; Under agitation drip 43.1g zero(ppm) water, after dropwising, again behind the isothermal reaction 3h; The beginning underpressure distillation, pressure-controlling boils off the small molecules that produces in the reaction process at 0.06MPa; Cool to room temperature, the adjustment solid content is 80%, obtains silicone resin midbody 230g.

C) performance:

The weight-average molecular weight of silicone resin midbody adopts GPC to detect, and the result is 2015; The hydroxy radical content of silicone resin midbody adopts the diacetyl oxide method to measure, and the result is 15%; The oxyethyl group content of silicone resin midbody adopts perchloric acid acetyl method to measure, and the result is 3%; R/Si=1.34; Ph/Me=0.44.

3) preparation of organic-silicon-modified saturated polyester

A) form:

The silicone resin midbody of 80% solid content of above-mentioned steps 2 preparations: 100g

B) preparation technology:

The poly-hydroxy branching saturated polyester that above-mentioned steps 1 is obtained; Silicone resin midbody that above-mentioned steps 2 obtains and the adding of 2g stannous octoate are equipped with in the reactor drum of heating, condensation and nitrogen protection device; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 80%, obtains organic-silicon-modified saturated polyester resin 260g.

4) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 80% solid content of above-mentioned steps 3 preparations: 100g;

Pigment Yellow 73 180 (CAS77804-81-0): 15g;

Phthalocyanine green 7 (CAS1328-53-6): 5g

Propionic acid-3-ether ethyl ester (EEP): 5g;

Divalent ester mixture (DBE): 2g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 2 non-viscous paint

Embodiment 3

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 57.2g (0.55mol);

The 2-methyl isophthalic acid, 3 Ucar 35 31.5g (0.35mol);

TriMethylolPropane(TMP) 13.4g (0.1mol);

M-phthalic acid 141.1g (0.85mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.4g metatitanic acid four isobutylates then, heating also is that heating is 4 hours under 200 ℃, heats 2 hours down at 230 ℃, under 250 ℃, heats 2 hours successively in temperature; Reach 95% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 352g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance:

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 180mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 2342.

2) the silicone resin midbody is synthetic

A) form

Monomethyl triethoxyl silane: 69.1g (0.36mol)

Dimethyldiethoxysilane: 34.0g (0.21mol)

One phenyl triethoxysilane: 109.24g (0.43mol),

B) preparation technology

After in the reactor drum that prolong, TM, tap funnel and whisking appliance are housed, adding siloxanes and 5.5mmol hydrochloric acid successively, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃ by proportioning; Under agitation drip 42.7g zero(ppm) water, after dropwising, again behind the isothermal reaction 3h; The beginning underpressure distillation, pressure-controlling boils off the small molecules that produces in the reaction process at 0.06MPa; Cool to room temperature, the adjustment solid content is 60%, obtains silicone resin midbody 322g.

C) performance:

The weight-average molecular weight of silicone resin midbody adopts GPC to detect, and the result is 1744; The hydroxy radical content of silicone resin midbody adopts the diacetyl oxide method to measure, and the result is 20%; The oxyethyl group content of silicone resin midbody adopts perchloric acid acetyl method to measure, and the result is 2.5%; R/Si=1.21; Ph/Me=0.55.

3) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 250g;

The silicone resin midbody of 60% solid content of above-mentioned steps 2 preparations: 65g;

B) preparation technology:

The poly-hydroxy branching saturated polyester of 60% solid content that obtains of above-mentioned steps 1 preparation is equipped with in the reactor drum of heating, condensation and nitrogen protection device with the silicone resin midbody adding of above-mentioned steps 2 preparations; Add 4g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 241g.

4) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 3 preparations: 130g;

Pigment red 122 (CAS No:16043-40-6): 11g;

Phthalocyanine blue (CAS147-14-8): 19g

Silicon-dioxide: 4g;

Titanium oxide: 6g

Methyl isoamyl ketone (MIAK): 8g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 3 non-viscous paint

Embodiment 4

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 67.6g (0.65mol);

The 2-methyl isophthalic acid, 3 Ucar 35 27g (0.30mol);

TriMethylolPropane(TMP) 6.7g (0.05mol);

M-phthalic acid 136g (0.82mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 358g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 165mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 5987.

2) the silicone resin midbody is synthetic

A) form

Monomethyl Trimethoxy silane: 42.0g (0.28mol)

Dimethyldimethoxysil,ne: 18.7g (0.14mol)

One phenyltrimethoxysila,e: 123.0g (0.58mol),

B) preparation technology

After in the reactor drum that prolong, TM, tap funnel and whisking appliance are housed, adding siloxanes and 4.5mmol hydrochloric acid successively, begin to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃ by proportioning; Under agitation drip 31.7g zero(ppm) water, after dropwising, again behind the isothermal reaction 3h; The beginning underpressure distillation, pressure-controlling boils off the small molecules that produces in the reaction process at 0.06MPa; Cool to room temperature, the adjustment solid content is 60%, obtains silicone resin midbody 290g.

C) performance:

The weight-average molecular weight of silicone resin midbody adopts GPC to detect, and the result is 802; The hydroxy radical content of silicone resin midbody adopts the diacetyl oxide method to measure, and the result is 10.6%; The methoxy content of silicone resin midbody adopts perchloric acid acetyl method to measure, and the result is 7.4%; R/Si=1.14; Ph/Me=1.04.

3) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 167g;

The silicone intermediate of 60% solid content of above-mentioned steps 2 preparations: 140g

B) preparation technology:

The poly-hydroxy branching saturated polyester that obtains of above-mentioned steps 1 preparation and the silicone intermediate adding of above-mentioned steps 2 preparations are equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 4g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 50%, obtains organic-silicon-modified saturated polyester resin 284g.

4) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 50% solid content of above-mentioned steps 3 preparations: 100g;

Pigment yellow 13 9 (CAS36888-99-0:12g;

Phthalocyanine blue (CAS147-14-8): 4g

Silicon-dioxide: 4;

Titanium oxide: 8;

Divalent ester mixture (DBE): 10g.

B) preparation of non-viscous paint

Paint filler, organic-silicon-modified saturated polyester, dispersion agent and high boiling solvent are mixed, add grinding machine for grinding, obtain non-viscous paint to required particle diameter.

C) performance of non-viscous paint

The over-all properties of table 4 non-viscous paint

Embodiment 5

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 62.4g (0.60mol);

The 2-methyl isophthalic acid, 3 Ucar 35 31.5g (0.35mol);

TriMethylolPropane(TMP) 6.7g (0.05mol);

M-phthalic acid 136g (0.82mol);

B) synthesis step:

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 151mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 5124.

2) the silicone resin midbody is synthetic

A) form

Monomethyl Trimethoxy silane: 24.0g (0.16mol)

Dimethyldimethoxysil,ne: 42.9g (0.32mol)

One phenyltrimethoxysila,e: 110.2g (0.52mol),

B) preparation technology

After in the reactor drum that prolong, TM, tap funnel and whisking appliance are housed, adding siloxanes and 6.0mmol hydrochloric acid successively, begin to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃ by proportioning; Under agitation drip 32.8g zero(ppm) water, after dropwising, again behind the isothermal reaction 3h; The beginning underpressure distillation, pressure-controlling boils off the small molecules that produces in the reaction process at 0.06MPa; Cool to room temperature, the adjustment solid content is 60%, obtains silicone resin midbody 263g.

C) performance:

The weight-average molecular weight of silicone resin midbody adopts GPC to detect, and the result is 1044; The hydroxy radical content of silicone resin midbody adopts the diacetyl oxide method to measure, and the result is 6.6%; The methoxy content of silicone resin midbody adopts perchloric acid acetyl method to measure, and the result is 11.8%; R/Si=1.32; Ph/Me=0.65.

3) preparation of organic-silicon-modified saturated polyester

A) form:

B) preparation technology:

4) high temperature resistant non-viscous paint

A) form

Pigment yellow 13 9 (CAS36888-99-0:12g;

Phthalocyanine blue (CAS147-14-8): 4g

Silicon-dioxide: 4;

Titanium oxide: 8;

Divalent ester mixture (DBE): 10g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 5 non-viscous paint

Embodiment 6

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 72.8g (0.7mol);

The 2-methyl isophthalic acid, 3 Ucar 35 26.1g (0.29mol);

TriMethylolPropane(TMP) 1..34g (0.01mol);

M-phthalic acid 144.4g (0.87mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.5g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 190 ℃, heats 2 hours down at 230 ℃, under 240 ℃, heats 2 hours successively in temperature; Reach 91% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 354g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 194mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 2891.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 200g;

Watt gram silicone resin IC836:130g of 60% solid content;

B) preparation technology:

The silicone resin watt gram IC836 of the poly-hydroxy branching saturated polyester of 60% solid content that obtains of above-mentioned steps 1 preparation and 60% solid content added be equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 2g isocaprylic acid zinc and 2g stannous iso caprylate; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 280g.

3) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 2 preparations: 120g;

Phthalocyanine blue: 20g;

Silicon-dioxide: 5g;

Titanium oxide: 5g;

CoatOSil?3500：4g；

Silicone oil /350cst:4g;

Divalent ester mixture (DBE): 3g;

Isobutyl isobutyrate: 2g.

B) preparation of non-viscous paint

Paint filler, organic-silicon-modified saturated polyester, auxiliary agent and high boiling solvent are mixed, add grinding machine for grinding, obtain non-viscous paint to required particle diameter.

C) performance of non-viscous paint

The over-all properties of table 6 non-viscous paint

Embodiment 7

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 66.56g (0.64mol);

The 2-methyl isophthalic acid, 3 Ucar 35 27g (0.3mol);

Dihydroxy methylpropane 8.04g (0.06mol);

M-phthalic acid 142.76g (0.86mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.5g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 180 ℃, heats 2 hours down at 240 ℃, under 240 ℃, heats 2 hours successively in temperature; Reach 87% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 355g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 200mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 2109.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 183g;

The KR213:124g of silicone resin SHIN-ETSU HANTOTAI of 60% solid content;

B) preparation technology:

The KR213 of silicone resin SHIN-ETSU HANTOTAI of the poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation and 60% solid content added be equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 4g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 291g.

3) high temperature resistant non-viscous paint

A) form

Phthalocyanine green 7 (CAS1328-53-6): 5g;

Titanium oxide: 5g;

CoatOSil?3500：4g；

Divalent ester mixture (DBE): 2g.

Isobutyl isobutyrate: 4g

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 7 non-viscous paint

Embodiment 8

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 78g (0.75mol);

The 2-methyl isophthalic acid, 3 Ucar 35 15.3g (0.17mol);

TriMethylolPropane(TMP) 10.7g (0.08mol);

M-phthalic acid 146g (0.88mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.3g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 190 ℃, heats 2 hours down at 230 ℃, under 255 ℃, heats 2 hours successively in temperature; Reach 97% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 365g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 172mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 5431.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 175g;

The silicone resin KR9218:69g of SHIN-ETSU HANTOTAI of 60% solid content;

The silicone resin KR217:69g of SHIN-ETSU HANTOTAI of 60% solid content;

B) preparation technology:

The silicone resin KR217 of SHIN-ETSU HANTOTAI of the silicone resin KR9218 of SHIN-ETSU HANTOTAI of the poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation, 60% solid content and 60% solid content added be equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 2g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 266g.

3) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 2 preparations: 130g;

Phthalocyanine blue: 10;

Pigment red 122 (CAS No:16043-40-6): 15g

Titanium oxide: 4g;

CoatOSil?7510：2g；

Divalent ester mixture (DBE): 2g;

Ethylene glycol ether acetate (CAC): 8g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 8 non-viscous paint

Embodiment 9

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 81.12g (0.78mol);

The 2-methyl isophthalic acid, 3 Ucar 35 14.4g (0.16mol);

TriMethylolPropane(TMP) 8.04g (0.06mol)

M-phthalic acid 112.88g (0.84mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid then, 0.1g metatitanic acid four isobutylates and 0.2g tetrabutyl titanate; Heat also is that heating is 4 hours under 180 ℃, heats 2 hours down at 230 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 95% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 357g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 161mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 4821.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 192g;

The silicone resin KR9218:75g of SHIN-ETSU HANTOTAI of 60% solid content;

The DOW CORNING silicone resin Z-6108:50g of 60% solid content;

B) preparation technology:

Poly-hydroxy branching saturated polyester, the silicone resin KR9218 of SHIN-ETSU HANTOTAI of 60% solid content and the silicone resin KR217 of SHIN-ETSU HANTOTAI of 60% solid content with 60% solid content of above-mentioned steps 1 preparation; Add and be equipped with in the reactor drum of heating, condensation and nitrogen protection device, add 5g isocaprylic acid zinc, be warmed up to 120 ℃ of insulations 2 hours; High 160 ℃ of insulations 2 hours heat up; Last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 295g.

3) high temperature resistant non-viscous paint

A) form

Phthalocyanine blue: 12g;

Pigment Yellow 73 180 (CAS77804-81-0): 5g

Silicon-dioxide: 3g;

CoatOSil?7001：2g；

Divalent ester mixture (DBE): 8g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 9 non-viscous paint

Embodiment 10

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 77g (0.74mol);

The 2-methyl isophthalic acid, 3 Ucar 35 22.5g (0.25mol);

TriMethylolPropane(TMP) 1.34g (0.01mol);

M-phthalic acid 149g (0.9mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 366g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 160mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 4907.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 168g;

The silicone resin KR9218:70g of SHIN-ETSU HANTOTAI of 60% solid content;

The DOW CORNING silicone resin 249:72g of 60% solid content;

B) preparation technology:

Poly-hydroxy branching saturated polyester, the silicone resin KR9218 of SHIN-ETSU HANTOTAI of 60% solid content and the silicone resin KR217 of SHIN-ETSU HANTOTAI of 60% solid content with 60% solid content of above-mentioned steps 1 preparation; Add and be equipped with in the reactor drum of heating, condensation and nitrogen protection device, add 5g isocaprylic acid zinc, be warmed up to 120 ℃ of insulations 2 hours; High 160 ℃ of insulations 2 hours heat up; Last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 315g.3) high temperature resistant non-viscous paint

A) form

Pigment yellow 13 9 (CAS36888-99-0): 20g;

Phthalocyanine green 7 (CAS1328-53-6): 10g

CoatOSil?7510：2g；

CoatOsil?7602：4g；

Divalent ester mixture (DBE): 6g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 10 non-viscous paint

Embodiment 11

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 82.1g (0.79mol);

The 2-methyl isophthalic acid, 3 Ucar 35 13.5g (0.15mol);

TriMethylolPropane(TMP) 8.04g (0.06mol);

M-phthalic acid 134g (0.81mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 349g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 182mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 3115.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The silicone resin KR9218:80g of SHIN-ETSU HANTOTAI of 60% solid content;

The DOW CORNING silicone resin Z-6108:80g of 60% solid content;

B) preparation technology:

The DOW CORNING silicone resin Z-6108 of the silicone resin KR9218 of SHIN-ETSU HANTOTAI of the poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation, 60% solid content and 60% solid content added be equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 4g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours; High 160 ℃ of insulations 2 hours heat up; Last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 305g.

3) high temperature resistant non-viscous paint

A) form

Phthalocyanine blue: 15g;

Titanium oxide: 10g;

CoatOSil?7001：2g；

Silicone oil

/350cst:4g;

Divalent ester mixture (DBE): 6g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 11 non-viscous paint

Embodiment 12

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 59.2g (0.57mol);

The 2-methyl isophthalic acid, 3 Ucar 35 31.5g (0.35mol);

TriMethylolPropane(TMP) 10.7g (0.08mol);

M-phthalic acid 144g (0.87mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 334g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 152mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 2711.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 217g;

The silicone resin KR9218:40g of SHIN-ETSU HANTOTAI of 60% solid content;

The DOW CORNING silicone resin Z-6108:60g of 60% solid content;

B) preparation technology:

Poly-hydroxy branching saturated polyester, the silicone resin KR9218 of SHIN-ETSU HANTOTAI of 60% solid content and the silicone resin Z-6108 of DOW CORNING SHIN-ETSU HANTOTAI of 60% solid content with 60% solid content that obtains of above-mentioned steps 1 preparation; Add and be equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 4g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 320g.

3) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 2 preparations: 125g;

Pigment Yellow 73 180 (CAS77804-81-0): 14g;

Titanium oxide: 2g;

Silicon-dioxide: 3g;

CoatOSil?7001：2g；

Silicone oil

/350cst:4g;

Divalent ester mixture (DBE): 2g;

Ethylene glycol ether acetate (CAC): 2g;

Diethylene Glycol monobutyl ether acetate (DBA): 5g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 12 non-viscous paint

Embodiment 13

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 74.9g (0.72mol);

The 2-methyl isophthalic acid, 3 Ucar 35 18g (0.20mol);

TriMethylolPropane(TMP) 10.7g (0.08mol);

M-phthalic acid 139g (0.84mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 367g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 174mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 2855.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The silicone resin DOW CORNING 3037:80g of 60% solid content;

B) preparation technology:

The poly-hydroxy branching saturated polyester of 60% solid content that above-mentioned steps 1 is obtained and the silicone resin DOW CORNING of 60% solid content 3037 add and are equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 2g isocaprylic acid tin; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 310g.

3) high temperature resistant non-viscous paint

A) form

Phthalocyanine green 7 (CAS1328-53-6): 20g;

CoatOSil7001：6g；

Divalent ester mixture (DBE): 7g;

Ethylene glycol ether acetate (CAC): 3g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 13 non-viscous paint

Embodiment 14

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 62.4g (0.6mol);

The 2-methyl isophthalic acid, 3 Ucar 35 31.5g (0.35mol);

TriMethylolPropane(TMP) 6.7g (0.05mol);

M-phthalic acid 141g (0.85mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 355g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 157mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 2866.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The poly-hydroxy branching saturated polyester of 60% solid content of above-mentioned steps 1 preparation: 153g;

The silicone resin DOW CORNING Z-6108:150g of 60% solid content;

B) preparation technology:

The poly-hydroxy branching saturated polyester of 60% solid content that above-mentioned steps 1 is obtained and the silicone resin DOW CORNING Z-6108 of 60% solid content add and are equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 4g isocaprylic acid tin; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 305g.

4) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 3 preparations: 95g;

Pigment red 254 (CAS84632-65-5): 12g;

Silicon-dioxide: 10;

CoatOSil?7001：2g；

Silicone oil

/350cst:4g;

Diethylene Glycol monobutyl ether acetate (DBA): 2g;

Ethylene glycol ether acetate (CAC): 2g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 14 non-viscous paint

Embodiment 15

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 70.7g (0.68mol);

The 2-methyl isophthalic acid, 3 Ucar 35 19.8g (0.22mol);

TriMethylolPropane(TMP) 13.4g (0.01mol);

M-phthalic acid 138g (0.83mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 362g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 166mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 4202.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The silicone resin KR211:75g of SHIN-ETSU HANTOTAI of 60% solid content;

The silicone resin KR214:75g of SHIN-ETSU HANTOTAI of 60% solid content;

B) preparation technology:

Poly-hydroxy branching saturated polyester with above-mentioned 60% solid content that obtains; The KR214 of the silicone resin SHIN-ETSU HANTOTAI adding of the KR211 of silicone resin SHIN-ETSU HANTOTAI of 60% solid content and 60% solid content is equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 2g isocaprylic acid zinc and 2g stannous octoate; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 308g.

3) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 2 preparations: 90g;

Pigment Yellow 73 Y-139:6g

Pigment red R-254:7g

Pigment red R-122:8g

Titanium oxide: 1.8g;

Silicon-dioxide: 1.5g

CoatOSil?7001：2g；

Silicone oil

/350cst:4g;

Propionic acid-3-ether ethyl ester (EEP): 3g;

Divalent ester mixture (DBE): 4g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 15 non-viscous paint

Embodiment 16

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 72.8g (0.7mol);

The 2-methyl isophthalic acid, 3 Ucar 35 21.6g (0.24mol);

TriMethylolPropane(TMP) 8.04g (0.06mol);

M-phthalic acid 143g (0.86mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 353g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

The hydroxyl value of poly-hydroxy branching saturated polyester detects according to the said method of GB/T7193.2-1987, and the result is 163mgKOH/g, and the weight-average molecular weight of poly-hydroxy branching saturated polyester adopts GPC to detect, and the result is 4825.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The DOW CORNING silicone resin 233:67g of 60% solid content;

B) preparation technology:

The silicone resin DOW CORNING 233 of the poly-hydroxy branching saturated polyester of 60% solid content that obtains of above-mentioned steps 1 preparation and 60% solid content added be equipped with in the reactor drum of heating, condensation and nitrogen protection device; Add 4g isocaprylic acid zinc; Be warmed up to 120 ℃ of insulations 2 hours, the high 160 ℃ of insulations 2 hours that heat up, last cool to room temperature; Adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 285g.

3) high temperature resistant non-viscous paint

A) form

Pigment Yellow 73 Y-139:12g

Pigment red R-254:32g

Pigment red R-122:2g

Titanium oxide: 2.5g;

Silicon-dioxide: 1.2g

CoatOSil?3500：4g；

Methyl isoamyl ketone (MIAK): 6g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 16 non-viscous paint

Embodiment 17

1) poly-hydroxy branching saturated polyester is synthetic

A) form:

NSC 6366 78g (0.75mol);

The 2-methyl isophthalic acid, 3 Ucar 35 18g (0.20mol);

TriMethylolPropane(TMP) 6.7g (0.05mol);

M-phthalic acid 148g (0.89mol);

B) synthesis step:

With NSC 6366,2-methyl isophthalic acid, heating is equipped with in 3 Ucar 35, TriMethylolPropane(TMP) adding, in the reactor drum of condensation and nitrogen protection, is warmed up to 160 ℃ under the nitrogen protection, and polyvalent alcohol is melted; Add m-phthalic acid and 0.1g metatitanic acid four isobutylates then; Heat also is that heating is 4 hours under 200 ℃, heats 2 hours down at 240 ℃, under 260 ℃, heats 2 hours successively in temperature; Reach 98% of theoretical aquifer yield, be cooled to 160 ℃ at last, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, and cool to room temperature obtains the 364g solid content and be 60% poly-hydroxy branching saturated polyester.

C) performance of poly-hydroxy branching saturated polyester

Hydroxyl value: 165mgKOH/g, weight-average molecular weight is 2667.

2) preparation of organic-silicon-modified saturated polyester

A) form:

The silicone resin KR212:100g of SHIN-ETSU HANTOTAI of 60% solid content;

The DOW CORNING silicone resin 3074:40g of 60% solid content;

B) preparation technology:

Poly-hydroxy branching saturated polyester with 60% solid content of above-mentioned steps 1 preparation; The KR212 of silicone resin SHIN-ETSU HANTOTAI of 60% solid content and 3074 addings of the silicone resin DOW CORNING of 60% solid content are equipped with in the reactor drum of heating, condensation and nitrogen protection device, add 4g isocaprylic acid zinc, are warmed up to 120 ℃ of insulations 2 hours; High 160 ℃ of insulations 2 hours heat up; Last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains organic-silicon-modified saturated polyester resin 286g.

3) high temperature resistant non-viscous paint

A) form

The organic-silicon-modified saturated polyester resin of 60% solid content of above-mentioned steps 2 preparations: 96g;

Pigment Yellow 73 Y-139:3.8g

Pigment red R-254:7.2g

Pigment red R-122:4.6g

Titanium oxide: 2.2g;

Silicon-dioxide: 1.2g

CoatOSil?7001：2g；

Silicone oil

/350cst:4g;

Divalent ester mixture (DBE): 4g.

B) preparation of non-viscous paint

C) performance of non-viscous paint

The over-all properties of table 17 non-viscous paint

Claims

1. high temperature resistant non-viscous paint, this coating contains the organic-silicon-modified saturated polyester of 50～80 weight parts, 10～30 weight part high-temperature resisting pigment fillers and 5～10 weight part high boiling solvents; Wherein,

Described high boiling solvent is meant a kind of or two or more in divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and the methyl isoamyl ketone;

Described pigment is a kind of or two or more in pigment yellow 13 9, Pigment Yellow 73 180, Pigment red 254, phthalocyanine blue, phthalocyanine green 7 and the pigment red 122;

Described filler is titanium oxide and/or silicon-dioxide;

Described poly-hydroxy branching saturated polyester is to be reacted by 0.8～0.9 times polyvalent alcohol esterification of m-phthalic acid and m-phthalic acid amount of substance to obtain, and its hydroxyl value is 120～200mgKOH/g, and weight-average molecular weight is 2000～6000; Wherein, described polyvalent alcohol is by the NSC 6366 of 60～80 moles of %, the 2-methyl isophthalic acid of 15～35 moles of %, and the TriMethylolPropane(TMP) of 3 Ucar 35 and 1～10 mole of % is formed;

2. the described high temperature resistant non-viscous paint of claim 1 is characterized in that, the hydroxyl value of described poly-hydroxy branching saturated polyester is 140～180mgKOH/g, and weight-average molecular weight is 2000～5000.

3. the described high temperature resistant non-viscous paint of claim 1; It is characterized in that, the KR9218 of the IC836 of Wa Ke company of the KR214 of the KR211 that described silicone resin midbody is a company of SHIN-ETSU HANTOTAI, the KR212 of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI, the KR216 of company of SHIN-ETSU HANTOTAI, Wa Ke company, the KR213 of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI, the KR217 of company of SHIN-ETSU HANTOTAI, Dow Corning Corporation 233, Dow Corning Corporation 249,3074 and Dow Corning Corporation of the Z-6108 of Dow Corning Corporation, Dow Corning Corporation 3037 in a kind of or two or more.